Purification of fluids with nanomaterials

ABSTRACT

Disclosed herein is a nanostructured material comprising defective carbon nanotubes chosen from impregnated, functionalized, doped, charged, coated, and irradiated nanotubes, and combinations thereof. The defective carbon nanotubes contain a defect which is a lattice distortion in at least one carbon ring. Also disclosed is a method of purifying fluids, such as liquids, including water, as well as gases, including the air using, this nanostructured material.

This application claims the benefit of domestic priority to U.S.Provisional Patent Application Ser. No. 60/452,530 filed Mar. 7, 2003,U.S. Provisional Patent Application Ser. No. 60/468,109 filed May 6,2003, and U.S. Provisional Patent Application Ser. No. 60/499,375 filedSep. 3, 2003, all of which are herein incorporated by reference in theirentirety.

The present disclosure relates to a nanostructured material comprisingdefective carbon nanotubes chosen from impregnated, functionalized,doped, charged, coated, and irradiated nanotubes. The present disclosurealso relates to the purification of fluids, such as liquids and gases,using the nanostructured material. The present disclosure also relatesto the purification of water using the nanostructured material.

There are many procedures and processes to treat fluids for consumption,use, disposal, and other needs. Among the most prevalent arepasteurization to sterilize foodstuffs, chemical treatments to sterilizewater, distillation to purify liquids, centrifugation and filtration toremove particulates, decanting to separate two phases of fluids, reverseosmosis to desalinate liquids, electrodialysis to desalinate liquids,and catalytic processes to covert undesirable reactants into usefulproducts. Each of these methods is well-suited for particularapplications so usually a combination of methods is used for a finalproduct.

One promise of nanotechnology materials is that they will help do thingsmore cost-effectively than their traditional counterparts. In the areaof liquid purification, any technology that can lower the overall cost,simplify a process, and improve efficiencies would be very advantageous.

Many of these processes would be improved by using nanomaterialpurification technologies. Nanoporous materials would be useful toremove microorganisms, micron size particulates, and other very finematerials. Reverse osmosis membranes made with nanomaterials could helpimprove the flow of water through the membrane. Incorporating strongnanomaterials into any of the above processes would lower the weight ofall of these components. But two processes seem especially likely fornanomaterial fluid purification: sterilization and desalination.

Sterilization

There are many different technologies available for the sterilization ofliquid. Adsorption, chemical treatments, ozone disinfection, and UVirradiation all perform very well for the removal of pathogenicmicrobes. However, each of these technologies has limitations, includingoverall efficacy, initial & operating cost, byproduct risk, necessarypre-treatment of liquid, hazardous compounds used or produced, and otherlimitations.

Although chemical methods are the most widespread in use, they have anumber of shortcomings. Such drawbacks include increasingmicrobiological adaptation to their destructive effects (e.g.Cryptosporidium parvum), safety hazards associated with chlorine use andstorage, and environmental impact. UV is gaining in popularity but theliquid must be clear in order for it to be effective, it does not breakdown any biofilm formation, and it is very expensive to install andoperate.

In industrial and municipal applications such as water and wastewaterplants, the three most widely used methods of liquid sterilization are:ozone, chlorine, and ultraviolet irradiation. Recent publications of theU.S. Environmental Protection Agency have identified the pros and consof each method.

Ozone is more effective than Chlorine at destroying viruses andbacteria, has a short contact time (10–30 minutes) for effectiveness,leaves no harmful residuals as it breaks down quickly, and is generatedonsite so there are no transportation risks. On the other hand, at lowdosages ozone may not be effective, it is more complex than either UV orchlorine, it is very reactive and corrosive, it is toxic, capital costscan be high and power requirements can be high.

Chlorine is more cost-effective than ozone or UV, its residual canprolong disinfection, it is reliable and effective against a range ofpathogenic organisms, and it offers flexible dosing control. Chlorine,though, carries with it significant risks including the facts thatchlorine residual is toxic to aquatic life, chlorine is corrosive andtoxic, chlorine's oxidation of organic matter creates hazardouscompounds, and some parasitic species have shown resistance. Inaddition, chlorine can bind with natural organic material to createcarcinogenic compounds hazardous for consumption.

Ultraviolet irradiation has been used for some time because iteffectively inactivates most spores, viruses, and cysts, eliminatesrisks of handling chemicals, leaves no residual that can be harmful, isuser-friendly to operators, requires a very short contact time (20–30seconds) for effectiveness and requires less space. The downsides of UVirradiation include: that at low dosages it may not be effective; thatorganisms can sometimes reverse and repair UV damage; that tubes canfoul requiring frequent preventative maintenance; that turbidity canrender UV ineffective, the energy requirements are very high. Further,disposal of hazardous UV lamps can be expensive.

In response to the shortcomings of known disinfection methods, a numberof new approaches have been tried. For example, U.S. Pat. No. 6,514,413,which is herein incorporated by reference, discloses using a composite,bactericidal adsorption material. Such bactericidal adsorption material,however, have been shown to be prone to biofouling and bacterialgrow-through for continued reproduction. U.S. patent application Ser.No. 09/907,092 discloses a portable oxidant generator for generating achlorine or chlor-oxygen solution for sterilizing contaminated drinkingwater. U.S. Pat. No. 6,495,052 discloses a system and method fortreatment of water that introduces a bactericide into the water and thenremoves it prior to consumption. U.S. patent application Ser. No.10/029,444 discloses a method whereby water is subjected to light from alaser as means of disinfection.

Again, however, these approaches rely on high inputs of electricity,toxic chemicals, or long contact times for effectiveness. What is stillneeded is a method that has minimal energy requirements, utilizes notoxic chemicals, and requires a very short contact time, and can beembodied into a portable device.

Desalination

Desalination of liquids would be highly useful for drinking water,biological fluids, medicines, chemicals, petroleum and its derivatives,and many other liquids. In addition, desalination of water would bebeneficial since less than 0.5% of the Earth's water is directlysuitable for human consumption, agricultural, or industrial uses.Consequently, desalination is finding increasing favor throughout theworld to produce potable water from brackish groundwater and seawatersince it makes the other approximately 99.5% of the water available.

There are an estimated 4,000 water desalination plants worldwide with acombined capacity of over 3,500 million gallons per day (mgd). About 55%of this capacity is in the Middle East and 17% is in the U.S., many ofwhich are for industrial use. Desalinated water now accounts for about1.4% of the water consumed in the United States for domestic andindustrial purposes.

There are essentially five basic desalination methods: thermal, reverseosmosis, electrodialysis, ion exchange, and freezing. Thermal andfreezing processes remove fresh water from saline leaving behindconcentrated brine. Reverse osmosis and electrodialysis employ membranesto separate salts from fresh water. Ion exchange involves passing saltwater over resins which exchange more desirable ions for less desirabledissolved ions. Only thermal and reverse osmosis processes are currentlycommercially viable.

As explained in U.S. Pat. No. 5,217,581 and U.S. Pat. No. 6,299,735,which are herein incorporated by reference, thermal processes involveboiling or otherwise evaporating salt water and condensing the vapor asfresh water, leaving behind a more concentrated brine solution. Theenergy requirement for distillation is relatively high compared to othermethods. In part because the energy required for distillation does notincrease appreciably with increasing salinity of the feed water, it iswidely used in the Middle East to treat seawater.

As described in U.S. Pat. No. 3,462,362, reverse osmosis is a membraneprocess that employs the tendency for fresh water to pass through asemipermeable membrane into a salt solution, thereby diluting the moresaline water. The fresh water moves through the membrane as though therewere pressure on it, which is called osmotic pressure. By applying veryhigh pressure to saline water on one side of a semipermeable membrane,fresh water can be forced through the membrane in the direction oppositethat of the osmotic flow. This process is called reverse osmosis.Although it is energy intensive (to create the high pressure), theenergy requirements of reverse osmosis are generally lower than those ofdistillation although its use of feed water is more inefficient thanother methods. Additionally, the membranes are very expensive, delicate,and prone to fouling.

Desalination by electrodialysis is a membrane process that removescontaminants and salt from liquids by using an electric current to pullionic impurities through ion selective membranes and away from thetreated liquids. Two types of ion-selective membranes are used—oneallows passage of positive ions and one allows passage of negative ionsbetween the electrodes of an electrolytic cell. Electricity is used toovercome the resistance of the ion through the ion selective membrane.The greater the resistance the higher the power demand, and hence theenergy cost will increase as the resistance increases When an electriccurrent is applied to drive the ions, fresh liquid is left between themembranes. The amount of electricity required for electrodialysis, andtherefore its operating cost, increases with increasing salinity of feedliquid.

Ion exchange resins replace hydrogen and hydroxide ions with salt ions.A number of municipalities use ion exchange for water softening, andindustries commonly use ion exchange resins as a final treatmentfollowing reverse osmosis or electrodialysis to produce very pure water.The primary cost of ion exchange is in maintaining or replacing theresins. The higher the concentration of dissolved salts in the water,the more often the resins will need to be regenerated and consequentlyion exchange is rarely used for salt removal on a large scale.

Freezing processes involve three stages: partial freezing of the saltwater in which ice crystals of fresh water are formed, separating theseice crystals from the brine, and then melting the ice crystals (e.g.,U.S. Pat. No. 4,199,961). Freezing has some advantages over otherprocesses as it requires less energy and its low operating temperaturesminimize corrosion and scale formation problems. The energy requirementsof freezing processes are high and are generally comparable to those ofreverse osmosis. Freezing technologies are still being researched anddeveloped and are not widely deployed. Freezing technology is not acompatible technology for portable desalinization devices.

There have also been a number of capacitors invented for the purpose ofdesalination. U.S. Pat. No. 4,948,514 discloses a method and apparatusfor separating ions from liquid. U.S. Pat. No. 5,192,432 discloses asimilar “flow-through capacitor” method for separating ions from liquid.However, these devices have not found wide-scale use because they arenot economically viable.

SUMMARY OF INVENTION

The present disclosure solves the aforementioned problems as it relatesto fluid purification methods based on nanotechnology materials. Oneaspect of the present disclosure is related to a nanostructured materialcomprising defective carbon nanotubes chosen from impregnated,functionalized, doped, charged, coated, and irradiated nanotubes.“Nanostructured” refers to a structure on a nano-scale (e.g., onebillionth of a meter), such as on the atomic or molecular level.“Nanostructured material” is a material comprising at least one of theabove-mentioned carbon nanotube components. “Nanomembrane” is a membranecomposed of the nanostructured material. Defective carbon nanotubes arethose that contain a lattice distortion in at least one carbon ring. Alattice distortion means any distortion of the crystal lattice of carbonnanotube atoms forming the tubular sheet structure. Non-limitingexamples include any displacements of atoms because of inelasticdeformation, or presence of 5 and/or 7 member carbon rings, or chemicalinteraction followed by change in sp² hybridization of carbon atombonds.

Another aspect of the invention is directed to elongated nanotubesconsisting essentially of carbon, wherein the nanotube is distorted bycrystalline defects, similar to those described above. In thisembodiment, the nanotubes are distorted, due to the defects, to a degreethat the nanotubes, when treated, have significantly greater chemicalactivity that allow the nanotube to react with, or bond to, chemicalspecies that would not react with or bond to undistorted and/oruntreated nanotubes. As used herein, the term “fused,” or any version ofthe word “fuse” is defined as the bonding of nanotubes at their point orpoints of contact. For example, such bonding can be Carbon—Carbonchemical bonding including sp³ hybridization or chemical bonding ofcarbon to other atoms.

In one aspect of the invention, the carbon nanotubes are present in thenanostructured material in an amount sufficient to substantiallydestroy, modify, remove, or separate contaminants in fluid that comesinto contact with the nanostructured material. The carbon nanotubes aretreated to achieve such properties. For example, chemical treatments ofthe carbon nanotubes can lead to the resulting nanotubes having at leastone end which is at least partially open. Nanotubes having such ends canprovide unique properties, either from a fluid flow perspective or froma functionalization perspective, e.g., having the ability of that end tobe particularly functionalized, for example.

In another aspect of the invention, the material that is used toimpregnate, functionalize, dope, or coat the carbon nanotubes is presentin an amount sufficient to achieve active and/or selective transport offluids or components thereof into, out of, through, along or around thecarbon nanotubes. This material may comprise the same material that isselectively transported into, out of, through, along or around thecarbon nanotubes.

For example, a nanostructure material used to remove arsenic from fluid,can be first impregnated with arsenic ions. These arsenic ions arereferred to as the “target ion.” A “target ion” generally encompasses anion that is impregnated (functionalized, doped or coated) into thecarbon nanotube, and that is the same as the ion of the contaminantfound in the fluid to be cleaned or purified.

As used herein, “impregnated” means that the carbon nanotubes are atleast partially filled with the material of interest, which, as shownabove, may comprise the same ion of the contaminant to be removed fromthe contaminated fluid. By impregnating a target ion into the carbonnanotubes, the nanotubes, and indeed the nanostructure made of thenanotubes, are primed or “challenged” to accept and/or attract and/orthose same ions found within the contaminated fluid.

While the above example refers to impregnated ions, the same methodsapply for challenging or priming the carbon nanotubes with desired ionsby any of the described procedures, e.g., functionalization, doping,coating, and combination thereof. A doped carbon nanotube refers to thepresence of atoms, other than carbon, in the nanostructured material.

With respect to impregnation, an ion specific separation device composedof a target ion-impregnated carbon nanotube can be fabricated. For thisdevice, the impregnated nanotubes are fabricated such that an electronor phonon current can either be induced by electromagnetic, or acousticmeans or by direct electrical or physical connection, and have defectsites that can be opened through functionalization chemistry to createion channels.

In challenging the carbon nanotubes by at least partially filling carbonnanotubes with target contaminate ions, ion specific quantum wells willbe created within the hollow region of the nanotube due to the quasi-onedimensional nature of the carbon nanotube defined by its morphology.This will create a “pre-programmed” or ion specific trap when the ion ismoved or indexed through the nanotube. When the ion is moved within thenanotube, the ion specific trap is left behind, in the quasione-dimensional quantum structure of the nanotube.

As ionic contaminated fluid comes into contact with the treated“pre-programmed” nanostructured material containing the target ions, thetarget ion will be able to minimize its free energy by adsorbing andfilling the ion specific trap within the nanotube. The addition of thetarget ion in the nanotube will cause a change in resistance, which willtrigger an electric and/or phononic current response that will move atleast one ion through the nanotube and out of the system. The materialcan be programmed or reprogrammed depending on what ion the nanotube,nanostructured device has been filled with.

As the ion concentration changes, the device will not have to consumepower because power is only required when target ions are present. Thebuilt in self limiting process will take advantage of the fact that whenthere are no target ions in the fluid no power is required to removethem.

Depending on the contaminant to be removed from the contaminated fluid,the target material or the material that is used to impregnate,functionalize, dope, or coat the carbon nanotubes may comprise at leastone compound chosen from oxygen, hydrogen, ionic compounds, halogenatedcompounds, sugars, alcohols, peptides, amino acids, RNA, DNA,endotoxins, metalo-organic compounds, oxides, borides, carbides,nitrides, and elemental metals and alloys thereof.

The oxides comprise any well known oxide generally used in the art, suchas an oxide of carbon, sulfur, nitrogen, chlorine, iron, magnesium,silicon, zinc, titanium, or aluminum.

In one aspect, the nanostructured material comprises the carbonnanotubes being placed in, and optionally dispersed in viaultrasonication, a liquid, solid, or gaseous medium. The carbonnanotubes may be maintained in such a medium by a mechanical force or afield chosen from, mechanical, chemical, electromagnetic, acoustic, andoptic fields or combinations thereof. One of skilled in the art wouldunderstand that acoustic fields comprise certain frequencies of noiseinside a cavity to form standing waves that hold the carbon nanotubes ina substantially static position.

Similarly, an optical field may comprise a single or an active array ofoptical tweezers generated by passing laser light through a hologram.

The solid medium in which the carbon nanotubes can be found generallycomprises at least one component chosen from fibers, substrates, andparticles, each of which may comprise metallic, ceramic, and/orpolymeric materials. In a solid medium, the carbon nanotubes areinterconnected and/or connected to fibers, substrates, and particles,such as those having a diameter up to 100 microns, to form ananomembrane.

Particle size is determined by a number distribution, e.g., by thenumber of particles having a particular size. The method is typicallymeasured by microscopic techniques, such as by a calibrated opticalmicroscope, by calibrated polystyrene beads and by calibrated scanningforce microscope or scanning electron microscope or scanning tunnelingmicroscope and scanning electron microscope. Methods of measuringparticles of the sizes described herein are taught in Walter C.McCrone's et al., The Particle Atlas, (An encyclopedia of techniques forsmall particle identification), Vol. I, Principles and Techniques, Ed.Two (Ann Arbor Science Pub.), which is herein incorporated by reference.

In different aspects of the present invention, the polymeric material ofthe solid medium comprises single or multi-component polymers(advantageously where the multi-component polymers have at least twodifferent glass transition or melting temperatures), nylon,polyurethane, acrylic, methacrylic, polycarbonate, epoxy, siliconerubbers, natural rubbers, synthetic rubbers, vulcanized rubbers,polystyrene, polyethylene terephthalate, polybutylene terephthalate,Nomex (poly-paraphylene terephtalamide), Kevlar poly (p-phenyleneterephtalamide), PEEK (polyester ester ketene), Mylar (polyethyleneterephthalate), viton (viton fluoroelastomer), polyetrafluoroethylene,polyetrafluoroethylene), halogenated polymers, such as polyvinylchloride(PVC), polyester (polyethylene terepthalate), polypropylene, andpolychloroprene.

The at least two different glass transition or melting temperatures ofthe multi-component polymers described herein are measured by heating toa temperature at which the material has inelastic deformation.

In an aspect of the invention, the ceramic material of the solid mediumcomprises at least one of the following: boron carbide, boron nitride,boron oxide, boron phosphate, compounds having a spinel or garnetstructure, lanthanum fluoride, calcium fluoride, silicon carbide, carbonand its allotropes, silicon oxide, glass, quartz, aluminum oxide,aluminum nitride, zirconium oxide, zirconium carbide, zirconium boride,zirconium nitride, hafnium boride, thorium oxide, yttrium oxide,magnesium oxide, phosphorus oxide, cordierite, mullite, silicon nitride,ferrite, sapphire, steatite, titanium carbide, titanium nitride,titanium boride, and combinations thereof.

In another aspect of the invention, the metallic material of the solidmedium comprises at least one of the following elements: aluminum,copper, cobalt, gold, platinum, silicon, titanium, rhodium, indium,iron, palladium, germanium, tin, lead, tungsten, niobium, molybdenum,nickel, silver, zirconium, yttrium, and alloys thereof, including analloy of iron, i.e., steel.

The liquid medium in which the carbon nanotubes can be found includewater, oil, organic and inorganic solvents, as well as the liquid formof nitrogen and carbon dioxide.

The gaseous medium in which the carbon nanotubes can be found includethe air, or a gas chosen from argon, nitrogen, helium, ammonia, andcarbon dioxide.

One aspect of the present disclosure is related to the use of carbonnanotubes that have a scrolled tubular or non-tubular nano-structure ofcarbon rings. These carbon nanotubes are usually single-walled,multi-walled or combinations thereof, and may take a variety ofmorphologies. For example, the carbon nanotubes used in the presentdisclosure may have a morphology chosen from nanohorns, nanospirals,dendrites, trees, spider nanotube structures, nanotube Y-junctions, andbamboo morphology. Such shapes generally tend to add in the use of thecarbon nanotubes for nanomembranes. The above described shapes are moreparticularly defined in M. S. Dresselhaus, G. Dresselhaus, and P.Avouris, eds. Carbon Nanotubes: Synthesis, Structure, Properties, andApplications, Topics in Applied Physics. Vol. 80. 2000, Springer-Verlag;and “A Chemical Route to Carbon Nanoscrolls, Lisa M. Viculis, Julia J.Mack, and Richard B. Kaner; Science 28 Feb. 2003; 299, both of which areherein incorporated by reference.

As previously described, carbon nanotubes may be functionalized toachieve desired chemical or biological activity. As used herein, afunctionalized carbon nanotube is one that comprises inorganic and/ororganic compounds attached to the surface of the carbon nanotubes.

The organic compounds may comprise linear or branched, saturated orunsaturated groups. Non-limiting examples of such organic compoundsinclude at least one chemical group chosen from: carboxyl, amine,polyamide, polyamphiphiles, diazonium salts, pyrenyl, silane andcombination thereof.

Non-limiting examples of the inorganic compounds include at least onefluorine compound of boron, titanium, niobium, tungsten, and combinationthereof. The inorganic compounds as well as the organic compounds maycomprise a halogen atom or halogenated compound.

In an aspect of the invention, functionalized carbon nanotubes compriseany one or any combination of the above-described inorganic and organicgroups. These groups are generally located on the ends of the carbonnanotubes and are optionally polymerized.

For example, the functionalized carbon nanotubes can comprise anon-uniformity in composition and/or density of functional groups acrossthe surface of the carbon nanotubes and/or across at least one dimensionof the nanostructured material. Similarly, the functionalized carbonnanotubes can comprise a substantially uniform gradient of functionalgroups across the surface of the carbon nanotubes and/or across at leastone dimension of the nanostructured material.

According to one aspect of the disclosure, carbon nanotubes are charged,such as with an AC or DC electromagnetic field, to a level sufficient toachieve desired properties. Desired properties include facilitating thecoating of a surface of the nanotubes or aiding in the destruction,modification, removal, or separation of contaminants that are found influids that are in contact or in proximity to the carbon nanotubes.“Removal” is understood to mean at least one of the followingmechanisms: size exclusion, absorption, and adsorption.

In addition, charging may occur using any one of the following methods:chemical, irradiation, capacitive charging, or fluid flowing adjacentand/or through the carbon nanotubes. Charging of the nanotubes may occurprior to or simultaneous with the above-described functionalizationprocedure.

Charging the nanotubes tends to facilitate their coating with metallicand/or polymeric materials. Examples of such metallic materials that canbe used to coat the carbon nanotubes include gold, platinum, titanium,rhodium, iridium, indium, copper, iron, palladium, gallium, germanium,tin, lead, tungsten, niobium, molybdenum, silver, nickel, cobalt, metalsof the lanthanum group, and alloys thereof.

Examples of such polymeric material that can be used to coat the carbonnanotubes include multicomponent polymers (advantageously where themulti-component polymers have at least two different glass transition ormelting temperatures), nylon, polyurethane, acrylic, methacrylic,polycarbonate, epoxy, silicone rubbers, natural rubbers, syntheticrubbers, vulcanized rubbers, polystyrene, polyethylene terephthalate,polybutylene terephthalate, Nomex (poly-paraphylene terephtalamide),Kevlar poly (p-phenylene terephtalamide), PEEK (polyester ester ketene),Mylar (polyethylene terephthalate), viton (viton fluoroelastomer),polyetrafluoroethylene, halogenated polymers, such as polyvinylchloride(PVC), polyester (polyethylene terepthalate), polypropylene, andpolychloroprene.

When using irradiation to treat the carbon nanotubes and/or fuse thecarbon nanotube nanostructured material, at least one type of particlechosen from photons, electrons, nuclear, and ion particles impinge onthe carbon nanotube in an amount sufficient to break at least onecarbon—carbon and/or carbon-dopant bonds, to activate the nanostructure,or to perform ion implantation.

Contaminants that can be cleaned from fluids include pathogens,microbiological organisms, DNA, RNA, natural organic molecules, molds,fungi, natural and synthetic toxins (such as chemical and biologicalwarfare agents), heavy metals (such as arsenic, lead, uranium, thallium,cadmium, chromium, selenium, copper, and thorium), endotoxins, proteins,enzymes, and micro and nano-particle contaminants.

The present disclosure also relates to a method of purifying fluids,which includes both liquids and gases by removing at least one of thesecontaminants from fluid. In such a method, contaminated fluid iscontacted with the above described nanostructured material, e.g., thenanostructured material comprising defective carbon nanotubes chosenfrom impregnated, functionalized, doped, charged, coated, and irradiatednanotubes, and combination thereof.

According to a method described herein, the activated nanostructuredmaterial may be treated and/or activated with constituents that modifythe biological or chemical activity of the fluid to be cleaned.

In addition, the method allows for at least partially separatingcontaminants from the treated fluids to form distinct fluid streams ofcontaminants and treated fluid.

In one embodiment, the fluid to be cleaned is a liquid, such as water,natural and/or synthetic petroleum and its byproducts, biologicalfluids, foodstuffs, alcoholic beverages, and medicines.

With respect to petroleum products, one major problem is the latentgrowth of bacteria in the petroleum during storage. This has been aproblem particularly with aviation fuel. The presence of such bacteriacan severely foul and eventually ruin the fuel. Accordingly, a majorarea of concern in the area of liquid purification is for cleaningbacteria from natural and/or synthetic petroleum products. Naturaland/or synthetic petroleum and its byproducts include aviation,automotive, marine, and locomotive fuels, rocket fuels, industrial andmachine oils and lubricants, and heating oils and gases.

The biological fluids described herein are derived from an animal,human, plant, or comprise a growing broth used in the processing of abiotechnology or pharmaceutical product. In one embodiment, thebiological fluids comprise blood, human milk and components of both.

In another embodiment, foodstuffs comprise animal by-products, such aseggs and milk, fruit juice, natural syrups, and natural and syntheticoils used in the cooking or food industry, including, but not limited toolive oil, peanut oil, flower oils (sunflower, safflower), vegetableoil, and the like.

In addition to foodstuffs, one embodiment of the present inventioninvolves the treatment of alcoholic beverages. By its very nature, thefermentation of alcoholic beverages results in contaminants in thefinished product. For example, oxygen is one undesired contaminant ofthe wine making process. As oxygen can cause the wine to spoil while inthe bottle, sulfites are normally added to absorb or remove this excessoxygen. Due to health concerns, however, sulfites should be avoided. Oneaspect of the present invention includes treating wine to removeunwanted contaminants, such as oxygen, using the above-describenanostructure material. Because the process would eliminate orsubstantially reduce the need for sulfites in wine, the wine industrywould benefit from the purification process described herein.

Another aspect of the present invention includes a method of cleaningthe air to remove the above-mentioned contaminants.

The present disclosure also relates to a method of purifying water bycontacting contaminated water with an activated nanostructured materialdescribed herein. It has been demonstrated that contaminants, such assalts, bacteria and viruses, can be removed from water, to a level of atleast 3 logs (99.9%), such as at least 4 logs (99.99%), and at least 5logs (99.999%), and up to level of detection currently available, i.e.,up to 7 logs (99.99999%).

The contaminants again comprise pathogens, microbiological organisms,DNA, RNA, natural organic molecules, molds, fungi, natural and synthetictoxins, heavy metals (e.g., arsenic, lead, uranium, thallium, cadmium,chromium, selenium, copper, and thorium), endotoxins, proteins, enzymes,and micro and nano-particle contaminants. Also of interest is thedesalination of water (i.e., where the contaminants comprise salts).

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an optical image of sample 1: E. coli without carbon nanotube,nanostructured material (not sonicated; fixation after 48 hours).

FIG. 2 is an optical image of sample 2: E. coli without carbon nanotube,nanostructured material (sonicated; fixation after 48 hours).

FIG. 3 is an optical image of sample 3: E. coli with carbon nanotube,nanostructured material; sonicated; fixation within 3 hours.

FIG. 4 is in optical image of sample 4: E. coli with carbon nanotube,nanostructured material (sonicated; fixation after 48 hours).

FIG. 5 is in an AFM image of sample 2: E. coli without carbon nanotube,nanostructured material (sonicated; no fixation).

FIG. 6 is an AFM image of sample #3: E. coli with carbon nanotube,nanostructured material (sonicated; fixation within 3 hours).

FIG. 7 is an AFM image of sample #3: three dimension transformation ofFIG. 6.

FIG. 8 is an AFM image of sample #3: E. coli with carbon nanotube,nanostructured material (sonicated; fixation within 3 hours).

FIG. 9 is an AFM image of sample #3: three dimension transformation ofFIG. 8.

FIG. 10 is AFM image of Sample #4: E. coli with carbon nanotube,nanostructured material (sonicated; no fixation).

FIG. 11 is an AFM image of sample #4: three dimension transformation ofFIG. 10.

FIG. 12 is a photograph showing a vertical nanotube at rest (left) andvibrating (right) due to fluid flow.

FIG. 13 is a micrograph of the edge of a nanostructured materialattached to a 20 micron metal mesh superstructure.

FIG. 14 is a micrograph showing nanotubes in a pore of a supportingsuperstructure (cellulose acetate) wrapping themselves around the fibersof the support structure.

FIG. 15 is a micrograph of the torn edge of a carbon nanotubenanostructured material.

FIG. 16 is a micrograph of a fused monolayer of carbon nanotubenanostructured material stretched and fused to support wires spanning a25×25 micron opening.

FIG. 17 is a photograph of self woven carbon nanotube nanostructuredmaterial.

FIG. 18 is a micrograph of freestanding carbon nanotubes fused at theintersection points to form a nanostructured material.

FIG. 19 is a micrograph of freestanding, self woven nanostructuredmaterial.

FIG. 20 is a simulation of fluid flow dynamics around a carbon nanotubesin a nanostructured material.

FIG. 21 is an image showing the results of a bacteria removal test.

DETAILED DESCRIPTION OF INVENTION

Fluid Sterilization

As described herein, fluid sterilization incorporating nanostructuressuch as carbon nanotubes, metallic oxide nanowires, and metal nanowiresis believed to be a result, at least in part from, in the formation of aunique nanoscopic kill zone that uses focused forces to kill microbesand other pathogens.

For example, it is believed that during sterilization of fluids,microorganisms come into contact with the nanomaterial described herein,causing focused forces to be applied to the microorganisms which breakopen cell membranes and cause internal cellular damage, thus destroyingthe microorganisms or destroying their ability to reproduce. In thisway, liquids can be sterilized from microorganisms. Commonmicroorganisms are 1–5 microns long and as such are at least 100 timeslarger than a nanostructure such as carbon nanotubes. Known examples ofthese organisms include E. coli, Cryptosporidium parvum, Giardialamblia, Entamoeba histolytica, and many others.

Due to the large size differences, forces on the nanoscopic scale, canbe applied that are many times, e.g., by orders of magnitude, moreconcentrated than those based on microscopic technologies. In much thesame way that focused light gives the intensity to a laser, focusedforces give the intensity to nanoscale destruction of microbes. Thus,mechanical and electrical forces that are on other scales either toosmall to be effective or very energy-intensive, on the nanoscale can beused to effectively and efficiently destroy microorganisms.

Mechanisms believed to be capable of destroying microorganisms in thisnano-regime can act independently or in concert with one another.Non-limiting examples of such mechanisms include:

-   -   Mechanical destruction of the cell wall through focused forces,        much like a pin breaking a balloon;    -   Vibrational waves causing internal cellular damage to the DNA,        RNA, proteins, organelles, etc.;    -   Vibrational waves causing damage to the cell wall and transport        channels;    -   Van der Waals forces;    -   Electromagnetic forces;    -   Damaging of the cell walls and DNA through the disruption of        hydrogen bonding in the vicinity of nanostructures; and    -   Bubble cavitations from shockwaves in the liquid which damage        the cell structure.

Since the osmotic pressure within a typical microbial cell is higherthan that of the surrounding fluid, assuming non-physiologicalconditions, even slight damage to the cell wall can cause total ruptureas the contents of the cell flow from high to low pressure.

MS2, which is commonly used as a surrogate in assessing treatmentcapabilities of membranes designed for treating drinking water, is asingle stranded RNA virus, with a diameter of 0.025 um and anicosahedron shape. Its size and shape are similar to other water relatedviruses such as the poliovirus and hepatitis.

Liquid Desalination

A process of liquid desalination according to the present disclosure isalso based on nanomaterials such as carbon nanotubes, metallic oxidenanowires, and metal nanowires. One mechanism believed to be capable ofdesalinating liquid with nanomaterials is the creation of an ionicseparation gradient between two nanomaterial membranes. When onenanomaterial membrane carries a positive charge and the other membrane anegative charge, the charge difference between these two plates createsan ionic separation gradient that causes cations to migrate to one sideof the zone and anions to migrate towards the other. The tremendoussurface area on the nanomaterial membranes is used to create very highcapacitance, enabling the creation of a very efficient ionic gradient.

A desalination unit could incorporate two or more parallel layers ofsupported conductive nanomaterial membrane that are electricallyisolated from each other. This layered nanostructured material may beassembled at the intersection of a Y junction channel. The two or morelayers may be electrically charged, in a static mode, or in an activemode in which the charge on each plate sequentially indexes frompositive to neutral to negative to neutral—one positively and onenegatively—to create either a salt trap between them or toelectronically create a moving capacitor in the structure causing thesalt to migration in a different direction than the flow of the water.The concentrated salt water would be channeled out one leg of the Yjunction and the fresh water out the other.

The geometry, capacitance, and morphology of the device may be optimizedfor the hydrodynamic flow using complex analysis such as method ofresidues, fitness functions and optimization algorithms. The base unitof the device will be a variant on the wide junction geometry in whichmost of the liquid will continue to flow along the main channel while asmaller quantity of liquid is taken out through the outlet channel.

Many such base units may be used in parallel and/or series to reduce thesalt concentration and increase total liquid processed. To furtherconcentrate the salt-liquid runoff it is envisioned to use a heat pumpto cool the near super-saturated salt liquid and to heat the incomingraw liquid. Such a system can be actively monitored to ensure properconcentration before cooling is applied. Salt crystallization will occurwhen the solution is cooled because the saturated solution willtransition into a super-saturated state more quickly in coldertemperature. In salt water, this will have the effect of speeding thecrystallization of the salt in the brine.

The final products of the desalination process will be a nearly saltfree liquid, such as removing contaminants, including but not limited tocrystallized salts or a concentrated brine mixture, to a level of atleast log 4 (99.99%) and up to and including log 7 (99.99999), withintermediate levels of log 5 and log 6 purity. In one embodiment, arefrigerated brine holding tank will speed crystallization and allow anyremaining liquid to be put through the process again.

According to one aspect of the present disclosure, surfaces susceptibleto biomaterials and other impurities or contaminants can be coated in alayer of nanomaterial to prevent the growth of microbes. Non-limitingexamples of such nanomaterials include functionalized nanotubenanostructured material that have been functionalized with elements orcompounds having antibacterial properties, such as silver, or aluminumoxide.

The invention further relates to methods to the manufacture thenanostructure materials described herein. Such methods include anorganic solvent evaporation process, a metallic oxide nanowire process,a geometric weave process, a vacuum filtration process, and ananostructure polymerization process. Each of these processes can createa nanostructure with nanomaterials embedded on them or composed of them.And each of these membranes enables the fluid purification treatmenttechnologies disclosed herein.

In one embodiment, membranes made according to the present disclosurehas high permeability to allow for high fluid flow rates. Thepermeability of a nanomaterial membrane is generally controlled by itsthickness and fiber density. Accordingly, an ultrathin, ultrastrongnanomaterial membrane of low fiber density will be much more transparentto the flow of fluids than a thick nanomaterial membrane would be.Therefore, one embodiment of the present invention is directed to afused nanomaterial membrane primarily composed of high strength carbonnanotubes.

To enhance its structural support and binding to other entities, theentire nanomaterial membrane can be coated with a metal, a plastic, or aceramic. Defects can be removed from the nanomaterial membrane bychemical, electrical, thermal, or mechanical means to enhance itsstructural integrity.

The entire nanomaterial membrane can be stimulated with static ordynamic electromagnetic fields to cause specific absorption or rejectionof certain molecules when fine tuned. High-frequency electricalstimulation can create an ultrasonic self-cleaning effect. By takingadvantage of the strength, Young's modulis, conductivity, andpiezo-electric effect of the nanotube, nanostructured material one canstimulate the material as a whole to vibrate, and to eject contaminatesfrom the surface, so as to reduce fouling.

The starting carbon nanotubes generally contain residual iron particlesor other catalytic particles that remain after production of thenanotubes. In certain embodiments, it is desired to wash the carbonnanotubes with a strong oxidizing agent such as acids and/or peroxidesor combinations there of before forming a nanostructured material. Uponwashing with a strong oxidizing agent, the iron generally found in thecarbon nanotubes is oxidized to Fe++ and Fe+++. In addition, acidwashing has the benefit of removing amorphous carbon which interfereswith the surface chemistry of the nanotube.

It is believed that the passivated, or positively charged iron plays arole in the removal of micro organisms which are known to have a netnegative charge. Under this theory, the micro-organisms are attracted tothe functionalized positively charged nanotube. The resulting electricfield of the now charged carbon nanotubes, which are partially filledand doped with iron, will destroy biological pathogens. Any positivelycharged hydrogen ions left over from the acid wash and trapped insidethe nanotube will also contribute to the electric field.

It is also thought that this acid washing procedure contributes to thehigh degree of hydrophilicity of these functionalized carbon nanotubesand the resulting carbon nanostructured material. The washed carbonnanotubes are generally fabricated into a nanostructured material usingone of the following processes. It is noted that any one of thefollowing processes, as well as those described in the Examples, can beused to create a nanostructured material described herein, whether multior monolayered.

Organic Solvent Evaporation Process

In the Organic Solvent Evaporation Process, a nanostructure material,such as a sterilization membrane, can be made by bonding nanomaterialswith an adhesive. Examples of adhesives are chemical adhesives, such asglue, metallic adhesives, such as gold, and ceramic adhesives, such asalumina. Examples of nanomaterials are carbon nanotubes, silicon andother metallic nanowires, and metallic oxide nanowires.

According to this process, carbon nanotubes can be mixed with a solvent,such as xylene. In one embodiment, this dispersion is next be placed inan ultrasonic bath for 5–10 minutes to de-agglomerate the carbonnanotubes. The resulting dispersion is next poured onto fiber paper toallow the organic solvent to evaporate, optionally with the addition ofmoderate heating. Upon evaporation, the carbon nanotubes deposit on thefiber paper. Additionally, other polymeric materials may be added to theorganic solvent to enhance the resulting structure's mechanicalstability; the concentration of this adhesive material can be at0.001–10% of the weight of the solvent used.

Metallic Oxide Nanowire Process

In another aspect of the present disclosure, a sterilization membrane ismade with metallic oxide nanowires. In this type of process, metalmeshes are heated to a temperature ranging from 230–1000° C. in anoxidative environment to create metallic oxide nanowires on the metalwires of the metal mesh. The metal meshes may comprise a metal chosenfrom copper, aluminum, and silicon. The metallic oxide nanowires can bein a size ranging from 1–100 nanometers in diameter, such as 1–50nanometers in diameter, including 10–30 nanometers in diameter.Advantageously, the surface of the mesh is abraded to provide surfacetexture to accept and hold the nanotube aliquot deposition to createbetter substrate attachment.

A membrane made according to this process may be used by itself tosterilize liquid, treated to strengthen its overall structure, or coatedwith carbon nanotubes or other nanostructures for further activity. Inthe coatings of carbon nanotubes, solutions of well-dispersed single ormulti-walled carbon nanotubes are passed through the mesh where theyadhere to the metallic oxide surface. This resulting mesh may or may notbe treated thermally, mechanically (e.g., such as by hydraulicpressure), chemically, or through rapid laser heating to enhancestructural integrity. It also may or may not be coated with metal,ceramic, plastic, or polymers to enhance its structural activity. Theresulting mesh may also be subjected to this nanotube solution treatmenta number of times until the proper design criteria are reached. Furthermodification to the carbon nanotubes and/or support of this membrane canbe made to functionalize the materials so that they chemically reactwith biological molecules to destroy, modify, remove, or separate them.

In this process, metal meshes, such as copper meshes are placed in achemical vapor deposition chamber in an oxidative environment. Thereaction zone is heated to a temperature ranging from 230–1000° C. tocause creation of metallic oxide nanowires while the chamber is in anatmosphere for a period ranging from 30 minutes to 2 hours. In certainembodiments, a dispersion of carbon nanotubes in liquid can then passedthrough the formed structure. After this treatment, the entire structurecan be thermally annealed in vacuum at 1000° C. to strengthen theoverall structure. The carbon nanotubes can optionally be treated in asolution of nitric and sulfuric acids to create carboxyl functionalgroups on the carbon nanotubes.

Deposition Process

In this process, a sterilization membrane can be made by vacuumdeposition of carbon nanotube dispersions to lay down layers of carbonnanotubes on at least one substrate. Ultrasonication may be used to aidin dispersing and/or deagglomerating carbon nanotubes during deposition.

An envisioned process of the deposition method comprises placing carbonnanotubes in a suitable organic solvent or liquid and ultrasonicating todisperse the carbon nanotubes during deposition. The solution can beplaced in a vacuum filtration device equipped with ultrasonication tofurther ensure that the carbon nanotubes are deagglomerated. Thenanomaterial in the solution may be deposited on to a substrate whoseporosity is small enough to trap carbon nanotubes but larger than themicroorganisms to be removed from the contaminated fluid. The resultingNanoMesh™ can be removed with the help of using a supporting metal meshto maintain flatness during removal. The porous substrate used to trapthe carbon nanotubes can also be removed by dissolving in acid or base,or oxidized to leave a free-standing carbon nanotube membrane.

According to an aspect of the present disclosure, the vacuum filtrationprocess may be modified by using electromagnetic fields to align thenanostructures during deposition. As in the previously describedprocess, the nanostructures are placed in a suitable solvent (organicsolvent or liquid), ultrasonicated to disperse them in the solvent,which is then placed in a vacuum filtration apparatus equipped with anultrasonic probe to keep them from becoming agglomerated duringdeposition. Unlike the previously described process, when the mixture isvacuum deposited on to a porous substrate, such as one having a poresize up to the centimeter size, an electromagnetic field is applied toalign the nanostructures during their deposition. This electromagneticfield can also be arbitrarily modulated in three space adjusted and toresult in a woven or partially woven—partially nonwoven structure. Theresulting membrane is then removed with the help of a supporting metalmesh and the entire membrane is immersed in acid to remove the initialsubstrate, which acted as a sacrificial support.

The vacuum filtration process may be modified to allow for the creationof multiple layers of nanostructures. A suspension of nanostructures canbe formed in an organic solvent above a substrate. For example, withvery low vacuum pressure the solvent is removed leaving behind a verythin layer of nanotubes on a steel mesh, such as a 20 micron steel mesh.This layer can then cured and dried. This process can repeated multipletimes in order to create several layers of NanoMesh™.

Air Laid Manufacturing Process

In this process, nanostructures can be dispersed evenly, whether in agas or a liquid solution. In a confined chamber, for example, a quantityof nanostructures is released as a fan to stir the gas to causedispersion of the carbon nanotubes in the chamber. This gas may also bemechanically modulated at frequencies sufficient to cause dispersion. Asthe carbon nanotubes are being added to the chamber they are charged toa voltage sufficient to overcome the attractive Van der Waals forces, bypassing the nanotubes through a high surface area electrode. This willprohibit agglomeration. The nanotube impregnated gas is now ready forgas phase deposition. By applying a pressure different passing the gasthough a grounded mesh electrode. The nanotubes will stick to thisgrounded mesh electrode. At this point the carbon nanotubenanostructured material is in its most fragile state. The nanostructuredmaterial can now be exposed to ionizing radiation to cause the structureto fuse together and/or to coat surface via chemical vapor deposition(CVD), plasma enhanced chemical vapor deposition PECVD, or physicalvapor deposition (PVD) processing techniques, or by chemical fusingtechniques. The surface can then be removed and exposed to a sputteringprocess sufficient to cover the nanostructures and cause them to locktogether. The resulting membrane can then be removed from the surface byreversing the charge of the surface causing the membrane to fall away.

Nanostructure Polymerization Process

In the polymerization process, a nanomaterial membrane is produced bylinking nanostructures to one another through polymer bonding.

An envisioned process of this method involves first ultrasonicating aquantity of nanostructures (such as carbon nanotubes) in an acidsolution. When using carbon nanotubes, the acid will act to cut thelengths of the nanotubes, to expose their ends, and allow carboxyl ions(COOH) to graft thereto. The resultant carboxyl functionalized productis then treated with concentrated acid to create carboxyl groups (COOH)which are more reactive for cross-linking reactions, such ascondensation. This COOH functionalized nanostructure is then reacted atthe carboxyl groups to cross-link two nanostructures together. Themixture is then allowed to react until an entire cross-linked network isformed into a fused nanomaterial membrane.

Method For Measuring Bacteria in Water

Multiple tests were performed on samples made using the methodsgenerally described above using bacteria, such as E. coli bacteria andMS-2 bacteriophage. MS-2 is a male specific, single stranded RNA virus,with a diameter of 0.025 μm and an icosahedron shape. Its size and shapeare similar to other water related viruses such as the poliovirus andhepatitis and it is a non-human pathogen.

The protocol used for testing removal of E. coli and MS-2 bacteriaphageand bacteria from water in the following examples were consistent withand generally adhered to: (i) Standard Operating Procedure for MS-2Bacteriophage Propogation/Enumeration. Margolin, Aaron, 2001 Universityof New Hampshire, Durham, N.H. and (ii) Standard Methods for theExamination of Water and Wastewater, 20^(th) Edition, Standard Methods,1998. APHA, AWWA, WEF, Washington, D.C. These standards generallyincluded the following procedure:

-   -   1) Placing the nanostructured material in a test housing        designed to hold the nanostructured material to be challenged.        Clamping the housing to prevent leakage of the challenge        solution.    -   2) Connecting a sterile effluent tubing to a sterile Erilenmeyer        flask using a rubber stopper.    -   3) Opening an influent port and introducing a challenge material        through open port.    -   4) After introducing the challenge, closing the influent port,        pumping, via a commercially available pump, a consistent flow        through the effluent hose connected to the housing.    -   5) Pumping continued until all challenge material passed into        the sterile Erlenmeyer flask, at which time the pump was turned        off.    -   6) Placing 0.1 ml of challenge material in 9.9 mls of water or        phosphate buffered saline solution (commercially available) in a        15 ml conical centrifuge tube.    -   7) Placing the 15 ml conical centrifuge tube into a commercially        available vortex mixer and mixing it for about 15 seconds.    -   8) Removing about 0.1 ml of the mixture from the centrifuge tube        and adding it to a second centrifuge tube containing 9.9 ml of        water or phosphate buffered saline solution (commercially        available), and repeating the vortex mixing described above.    -   9) Removing 0.1 ml of the mixture from the centrifuge tube and        placing it on a tryptic soy agar (TSA) plate, (Remel Cat. No.        01917), where it can be spread with a sterile spreader over the        agar surface. Drying the surface for 15 seconds before it is        placed into a commercially available incubator at 36° C. and        incubated for 18–24 hours.    -   10) After incubation, removing the plates from the incubator and        placing them on a back lit plate counter. Counting those plates        that appeared to have between 25–300 cfu/plate (1:10,000        dilution) per plate. The control and test plates were counted in        the same manner.    -   11) Recording the number of virus or bacteria counted and the        dilution factor at which they were counted, with an average of        the plate counts being multiplied by their corresponding        dilution factor and divided by the amount of dilution used per        plate. This calculation, which is shown below, gives the amount        of virus or bacteria in the original sample.

The following is a more detailed description of a procedure used inconducting testing with MS-2.

A 1% solution MgCl₂ (or CaCl₂) is first be prepared by adding to adesired amount of DI water MgCl₂ (or CaCl₂). A typical example is 1.0 gMgCl₂/99 ml DI water. This solution is autoclaved and cooled.

A preparation of Phosphate Buffered Saline Solution (1× PBS) is nextprepared by adding to a desired amount of DI water Phosphate BufferedSaline Powder Concentrate. A typical example is 4.98 g PBS/500 ml DIwater. This solution is also autoclaved and cooled.

A preparation of streptomycin/ampicillin antibiotic solution (Strep/Amp)is next made by adding to a desired amount of DI water StreptomycinSulfate. A typical example is 0.15 g Strep/100 ml DI water. AmpicillinSodium Salt is then added to the solution. A typical example is 0.15 gAmp/100 ml DI water. This solution is filtered thru 0.22 μm syringefilter into a sterile container.

A preparation of E. coli Stock Culture is made by first making a desiredvolume of Tryptic soy broth. The previously made streptomycin/ampicillinantibiotic solution is mixed with the T-soy in 1:100 ratio. (1.0 mlstep/amp/100 ml T-soy).

Next 1% solution of MgCl₂ is added in 1:200 ratio. (0.5 ml MgCl₂/100 mlT-soy), followed by the addition of E. coli in 1:10 ratio. (10 ml E.coli/100 ml T-soy). The E. coli strain used herein is the HS(pF amp)Rstrain (E. coli with an inserted strep/amp resistance plasmid). E. colistrain C3000, which commercially available (American Type CultureCollection (ATCC)) can also be used.

The T-soy broth/E. coli culture is then placed into a shaking water bathat 37° C. (or orbital shaker in a 37° incubator), shaking vigorously for2.5–3.0 hours (or at a time in which the E. coli reach mid-log phase intheir growth cycle). This shaking step is to provide oxygen to theentire culture so it does not become anaerobic and inhibit growth. Theculture is then from incubator and stored at 10° C.

MS2 Bacteriophage Propagation was performed by first adding liquidculture of MS2 (approx. 1×10¹⁰–1×10¹¹ MS2/500 ml T-soy broth) to theT-soy broth and then incubating at 37° C. for 12–18 hours. The MS2strain used was a commercially available specimen (ATCC (American TypeCulture Collection), catalog #15597-B1)).

The culture is transferred to an appropriate size centrifuge tube, andcentrifuged under the following conditions: 10,000 rpm, 4° C., for 10minutes. After centrifuging, the supernatant can be decanted, beingcareful not to disturb the pellet. The MS2 stock is generally stored at10° C.

MS2 Enumeration is generally performed in the following manner. A 1×Overlay is made by mixing the following in 1000 ml of DI water andbringing to a boil.

-   -   a. 15 grams T-soy broth    -   b. 7.5 grams bacto agar    -   c. 5 grams yeast extract    -   d. 2.5 grams NaCl    -   e. 0.075 grams CaCl₂

Four to Five ml of the overlay is next dispensed into test tubes andautoclave at 121° C. for 15 minutes, after which time the test tubes areremoved from the autoclave and placed into 57° C. water bath forimmediate use or stored at room temperature for future use. If placed instorage, the overlay will hardened, requiring it to be re-autoclaved.Overlay can only be re-autoclaved a few times until it becomes verydark, almost black, in color.

One skilled in the art would know how to perform 10 fold serialdilutions on sample in PBS to achieve a desired dilution point. Soonafter remove the previously described test tube containing the overlayfrom the water bath, approximately 0.1 ml of the desired sample dilutionand 0.2 ml of the previously described E. coli host can be fed is intothe overlay. About 30 μL of the streptomycin/ampicillin antibioticsolution can be added for the mixed culture samples. It is important tonote that the injection of 0.1 ml of diluted sample represents anadditional 10 fold dilution. Therefore, when 0.1 ml of the 10⁻¹ dilutionis placed in the overlay, the resulting dilution on the T-soy plate is10⁻². In order to plate a 10⁻¹ dilution, inject 0.1 ml of the originalundiluted sample into the overlay. In order to plate a 10⁰ dilution,inject 1.0 ml of the original undiluted sample into the overlay usingthe same volume of the E. coli host (0.2 ml).

Without shaking, the diluted sample and MS2 is mixed throughout theoverlay. The overlay and its contents are added onto a T-soy plate,which is swirled in a circular motion to evenly distribute the overlayacross the surface of the agar. After a few minutes, the overlay harden,at which time it is incubated at 37° C. for 12–18 hours.

When the incubation is complete, MS2 plaques will appear as circularclearing zones in the E. coli lawn.

Negative and positive controls are generally used in this assay. Thenegative control includes the addition of only the E. coli to theoverlay (no sample) to determine if the E. coli is growing properly, andif any phage or bacterial contamination is present. An additionalcontrol that can also be used to determine these factors can beperformed by placing a small volume of the E. coli host (no MS2 oroverlay) on a T-soy plate and examining the resulting colony morphology.

The positive control includes the addition of only the E. coli to theoverlay (no sample) and subsequent plating. Once the overlay is evenlydistributed across the surface of the plate, a small volume of MS2 stockis placed on various spots throughout the surface of the overlay. Afterincubation, the presence of plaques in these spots demonstrates that theE. coli host can effectively be infected by the MS2 phage.

Determining PFU/ml (Plaque Forming Units/ml) in original, undilutedsample:

${{PFU}\text{/}{ml}} = \frac{\#\mspace{14mu}{of}\mspace{14mu}{observed}\mspace{14mu}{plaques}\mspace{14mu}{on}\mspace{14mu}{plate}}{{Dilution}\mspace{14mu}{factor}\mspace{14mu}{of}\mspace{14mu}{the}\mspace{14mu}{plate}}$

For example, if 35 plaques were observed on a plate having a dilutionfactor of 10⁻⁸, the PFU would be:

$\frac{35\mspace{14mu}{plaques}}{10^{- 8}} = {3.5 \times 10^{9}\mspace{14mu}{PFU}/{ml}\mspace{14mu}{in}\mspace{14mu}{original}\mspace{14mu}{sample}}$

Using the methods described above, and as exemplified in the followingsamples, there is strong adherence forces between bacteria and carbonnanotube, nanostructured material. The bacteria adhered to the carbonnanotube nanostructured material surface at sonication. It is believedthat the same adherence of E. coli suspension occurs when it is passedthrough nanomesh of carbon nanotube nanostructured material.

In addition, it is believed that the integrity of the bacteria cell isdestroyed upon interaction with carbon nanotube, nanostructuredmaterial. For example, bacteria tests using the nanostructured materialdescribed herein showed a destructive mechanism in which the shell/cellwall was completely destroyed. This destruction apparently occurs due toa breech in the integrity of the cell wall, which leads to acatastrophic failure of the cell wall, due to the difference in theosmotic pressure between the interior of a complete cell and the osmoticpressure on the exterior of the cell. Thus, when the integrity of thecell wall/shell is compromised, those osmotic pressure differencesresult in disintegration of the bacteria.

For example, Example 3 shows the destruction of E. coli bacteria, asevidenced by the presence of free bacteria DNA and protein found in thefiltrate. Damaged cells are dissipated by water flow as seen in Example3. Therefore, not only does the inventive carbon nanotube nanostructuredmaterial completely destroy bacteria but the inventive material does notfoul due to the build up of bio burden, which should provide for alonger life than those materials currently used.

The invention will be further clarified by the following non-limitingexamples, which are intended to be purely exemplary of the invention.

EXAMPLE 1 Fabrication of an Activated Defective Nanostructured Material

An activated nanostructured material was made from commerciallyavailable purified carbon nanotubes. These nanotubes were placed in a 50ml conical centrifuge tube to which concentrated nitric acid was addedto a volume of 45 ml. The tube was shaken vigorously for 2–3 minutes tomix the acid and nanotubes, and then centrifuged at 2,500 RPM for fiveminutes to pellet the nanotubes.

A yellow supernatant was decanted and the nitric acid wash was repeated.The carbon nanotubes were then washed 2–3 times with water to reduce theacid concentration below a point at which the acid did not react withthe isopropanol used in the following steps.

100 mg of the nitric acid washed/water rinsed carbon nanotubes were nextadded to 400 ml of commercially available neat isopropanol andultrasonicated in a Branson 900B ultrasonicator 80% power until thecarbon nanotubes were well dispersed (about 10 minutes). The mixture wasfurther diluted by adding 2 liters isopropanol such that the totalvolume of the resulting mixture was 2.4 liters. This diluted mixture wasultrasonicated for an additional 10 minutes.

Next, 800 mg of a commercially available 200 nm diameter silicon oxidenano-fiber was homogenized in a commercially available blender at fullpower for 10 minutes in 500 ml of the commercially available neatisopropanol. The homogenized mixture was then diluted by adding anadditional 1 liter of commercially available neat isopropanol.

The previously prepared mixture of carbon nanotubes and silicon oxidenano-fiber was mixed and then quantity sufficient (Q.S.) amounts ofisopropanol was added to obtain 4 liters. This 4 liter solution was thenultrasonicated with a “Branson 900B ultrasonicator” at 80% power for 15minutes, which caused the carbon nanotube nanomaterial to uniformlydisperse.

The entire 4 liter solution was then deposited onto a 16 square incharea on a commercially available 5 micron polypropylene nonwoven fusedfabric. About half of the solution was passed through the polypropylenefabric under ½ in Hg of vacuum pressure. The remaining 2 liters of thesolution was then passed through the fabric under a pressure of 5 in Hguntil the remaining solution passed through the polypropylene fabric andthe carbon nanotube silicon oxide suspension was deposited on thefabric.

The resulting nanostructure material (called NanoMesh™) was removed fromthe fabricator and allowed to air dry at room temperature for 2 hrs toform an activated carbon nanotube, nanostructured material.

EXAMPLE 2 Purification Test of Nanostructured Material with E. coliBacteria

This example describes a purification test on water contaminated with E.coli bacteria stock culture, that was purchased from American TypeCulture Collection (ATCC).

A bacteria assay was conducted by challenging the carbon nanotubenanostructured material, made in accordance with Example 1, with achallenge of ((4×10⁷±2×10⁷ colony forming units per ml (cfu/ml)) of E.coli stock culture ATCC #25922, that was first reconstituted. Using asterile biological loop (commercially available) a loop of thereconstituted stock was removed and streaked on a commercially availableblood agar plate and incubated for 12–18 hours at 36° C. The culture wasthen removed from the incubator and examined for purity.

Using a sterile biological loop (commercially available) a loop of theincubated culture was removed and placed in 10 ml of sterilecommercially available Tryptic soy broth (Remel cat. No. 07228). E. coliwas then grown in the resulting trypticase-soy broth overnight to form astock culture of 1×10⁹ cfu/ml. 1 ml of the stock culture was added to100 ml of water used for the challenge test. The resulting challengedwater was then passed through the carbon nanotube, nanostructuredmaterial, made in accordance with Example 1.

The test was performed in accordance with the “Standard Methods for theExamination of Water and Waste Water” cited above. Results of testsfollowing the protocols described above established consistent removalof E. coli bacteria greater than 6 logs (>99.99995%) to greater than 7logs (>99.999995%) when the challenge material was passed through thecarbon nanotube, nanostructured material, made in accordance withExample 1.

The test results established removal rates which exceeded EPA potablewater standards for removal of bacteria from water. The EPA standardsdictate 6 logs removal (>99.99995%) of E. coli bacteria to achievepotable water. Improved purification by greater log removals of E. colibacteria have been achieved in such tests, by challenging the carbonnanotube, nanostructured material, with higher concentrations of E. colibacteria challenge material, made as described above. Such tests withhigher concentrations confirm removal rates of greater than 7 log.Independent tests, using the test procedures described in this example,of the carbon nanotube nanostructured material, made in accordance withExample 1, establish this material as a complete barrier to E. colibacteria.

EXAMPLE 3 Chemical Analysis of Sterilized Post-Challenge Filtrate

This example describes the chemical analysis of filtrate from an E. colichallenge test, performed as described in Example 2, on the carbonnanotube nanostructured material, made in accordance with Example 1.This example provided verification of purification through destructionof E. coli bacteria passing through the inventive carbon nanotubenanostructured material. Evidence of purification through thedestruction of the contaminant, (E. coli bacteria) was established bythe presence of DNA and protein in the challenge filtrate.

A challenge test was run in accordance with Example 2, except that thecomposition of the challenge material was 1×10⁸ cfu/ml of E. coli. Atotal of 100 ml (total=1×10¹⁰ cfu) of this challenge solution was drawnthrough the carbon nanotube, nanostructured material using with ½ in Hgof vacuum pressure. A control filtrate was obtained by passing the E.coli challenge filtrate through a commercially available 0.45 micronMillipore filter. The resulting filtrates, of the control and thechallenge, were then analyzed with a commercially availablespectra-photometer to determine the presence of protein and DNA. Thetest challenge filtrate was not concentrated. However, the analysis ofthe filtrate with a commercially available spectra-photometer revealed40 μg/ml of DNA and 0.5 mg/ml of protein. Concentrations of protein andDNA at these levels in non-concentrated challenge filtrate were 6 timeshigher than the control test material. These concentrations confirmedthe destruction of the E. coli in the challenge by the carbon nanotubenanostructured material.

EXAMPLE 4 Purification Test on Water Contaminated with MS-2Bacteriophage Virus

This example describes a purification test on water contaminated withMS-2 bacteriophage virus using the procedure described above and in the“Standard Operating Procedure for MS-2 BacteriophagePropagation/Enumeration, Margolin, Aaron, 2001, An EPA ReferenceProtocol.” The MS-2 bacteriophage virus is commonly used in assessingtreatment capabilities of membranes designed for treating drinking water(NSF 1998). The pressure challenges for this example were performed with100 ml challenge solutions using the protocols described above. The MS-2challenge materials were prepared in accordance with those stepsenumerated above.

In this test, eighty (80) membranes comprised of the carbon nanotubenanostructured material made in accordance with Example 1, werechallenged. The challenge material used was water contaminated with MS-2bacteriophage virus to the concentration of 4×10⁶+2×10⁶ pfu/ml.

Of the 80 units tested, 50 units achieved MS-2 removal of 5 logs(99.999%) or greater than 5 logs (>99.9995%). The remaining 30 unitsdemonstrated 4 logs (99.99%) or greater than 4 logs (>99.995%) removalof MS-2. While EPA standards recommend 4 logs removal of MS-2Bacteriophage to achieve potable water, it is believed that bettersensitivity (higher log removal) can be achieved by challenging withhigher log challenges of MS-2. Improved purification by greater logremovals of MS-2 Bacteriophage have been achieved in such tests, bychallenging the carbon nanotube nanostructured material, made inaccordance with Example 1, with higher concentrations of MS-2Bacteriophage challenge material, made as set forth above. Independenttests of the carbon nanotube nanostructured material, made in accordancewith Example 1, establish this material as a complete barrier to MS-2Bacteriophage.

EXAMPLE 5

Purification Test on Water Contaminated with Arsenic (As)

This example describes a purification test on water contaminated witharsenic. In this test, a stock solution of 150 parts per billion arsenicin 100 ml of water was passed through the carbon nanotube,nanostructured material, made in accordance with Example 1. A sample ofthe as-treated water was analyzed according to the EPA Method #SM183113B. The analysis of the challenge filtrate confirm a reduction ofthe arsenic level by 86%±5%; after passing the challenge as-treatedwater, one time through the inventive carbon nanotube nanostructuredmaterial.

EXAMPLE 6 Removal of Contaminants from Aircraft Fuel

A sample of contaminated jet fuel (JP8) was obtained from a 33,000gallon storage tank located at the United States Air Force Researchfacility at the Wright Patterson Air Force base. After collection, thesample was cultured on trypticase-soy agar and found to contain threetypes of bacteria: two bacillus species and one micrococcus species. Thesample was separated in two container of 2 liters each. Both containerspresented two distinct layers, jet fuel on top and water on the bottom.Container A contained a heavy contaminated growth layer at the interfacebetween the water and the fuel. Container B only showed slightcontamination. The challenge test bacteria were obtained from theinterface of the fuel and water from Container B.

After being homogenized, which was accomplished by shaking the challengetest fuel/water/bacteria vigorously for 1 minute, 200 ml of thefuel/water/bacteria challenge mixture was passed one time, using 3inches of Hg of vacuum pressure, through the carbon nanotube,nanostructured material, made in accordance with Example 1.

The fuel/water/bacteria challenge filtrate sample was allowed toseparate into its fuel—water components, and four test samples wereobtained from each component. Each test sample was plated on agar.Samples were then incubated to analyze bacteria growth at 37° C. andsamples were incubated at room temperature to analyze mold growth. Nobacteria or mold culture growth was observed on the challenge filtratetest plates after incubating the samples for 24 and 48 hours. Thecontrol samples presented vigorous colonies of bacteria and mold growthafter incubation at 24 and 48 hours. The results confirm that the carbonnanotube nanostructured material, made in accordance with Example 1, wasa complete barrier to bacteria in fuel for it accomplished removal ofbacteria and mold from the fuel beyond the limits of measuring withtesting protocols.

EXAMPLE 7 A Study of E. Coli Interaction with Carbon NanotubeNanostructured Material

The carbon nanotube nanostructured material, made in accordance withExample 1 was rinsed 6 times with DI water. The rinsed carbon nanotubenanostructured material was diluted to a concentration of 10,000 ppm inDI water.

Preparation of E. Coli Suspension:

A culture of E. coli as described above, was prepared to a concentrationof 5×10⁹ CFU/ml in pure water.

Preparation of Control Slide Sample #1:

One drop of the prepared E. coli suspension was placed on a commerciallyavailable glass microscope slide (American Scientific Products, MicroSlides, plain, Cat. M6145, size 75×25 mm) that was cleaned with sulfuricacid and rinsed with DI water. The drop of E. coli suspension wassmeared and allowed the to air dry, and refrigerated at 4 degreesCelsius for 48 hours. The prepared slide was heat fixed by passingthrough a flame in a manner known to the art.

Preparation of Test Suspensions:

The remaining E. coli suspension, prepared as outlined above, was thendivided in two equal parts by separating into two Erlenmeyer flasks(Suspension #1 and #2).

Preparation of Suspension #1:

Suspension #1 was diluted with DI water to a concentration of 2×10⁹CFU/ml of E. coli.

Preparation of Suspension #2:

Carbon nanotube, nanostructured material, made in accordance withExample 1, was added to Suspension #2. Suspension #2 was diluted with DIwater to the same concentration of E. coli as Suspension #1. Theconcentration of carbon nanotube nanostructured material, made inaccordance with Example 1, was 625 ppm.

Ultrasonication and Centrifuging:

Suspensions #1 and #2 were simultaneously ultrasonicated with aBranson-2510 sonicator for 3 min. These suspensions were centrifuged ina commercially available centrifuge at 2500 rpm for 2 minutes to pelletthem, and subsequently decanted leaving 1 ml of supernatant behind (andto suspend the pellet in Suspension #1 and #2). The pellet of Suspension#1 and #2, was then used in samples described below.

Sample #2:

Sample 2 was prepared by placing a drop of Suspension #1 was placed on aglass slide described above, and refrigerated for 19 hours. After beingrefrigerated for 19 hours, an atomic force microscope (AFM) was used toinvestigate the sample without fixation. Sample #2 was then placed in arefrigerator for 24 hours at the same temperature noted above. Afterbeing refrigerated for 24 hours, Sample #2 was thermally fixed, bymethods know in the art. Sample #2 was stained by methods know to theart, using with Gram Crystal Violet dye. Light microscopy wassubsequently investigated.

Sample #3:

Sample 3 was prepared by placing (and smearing) a drop of Suspension #2on a glass slide. Thermal fixation was performed within 3 hours afterultrasonic treatment. Stain Sample #3, by methods know to the art, usingGram Crystal Violet dye. Sample #3 was placed in a refrigerator at thesame temperature noted above. After 19 hours, Sample #3 was removed fromthe refrigerator and analyzed with an AFM without fixation. Sample #3was placed back in the refrigerator at for 24 hours, after which timelight microscopy was conducted.

Sample #4:

Sample #4 was prepared in the manner described for Sample #2, with theexception that Suspension #2 (and not Suspension #1) was used.

Light Microscopy

Samples were investigated under Olympus light microscope at 1000×magnification and under immersion oil. Digital images were made withOlympus DP10 CCD.

Both samples #1 and #2 (suspension of bacteria without carbon nanotubenanostructured material) demonstrated the image of E. coli cellsuniformly distributed over the entire surface of the slide (see FIGS. 1and 2). The images illustrate bacteria as having well-defined edgessuggesting that the bacteria cells were intact. No changes in theirshape were found after 2 days stored in a dry state in the refrigerator.There were no detectable changes in bacteria cell morphology betweensamples that were heat fixed and stained 3 hours after samplepreparation or heat fixed and stained after 2 days stored in a dry statein the refrigerator.

Sample #3 demonstrated complete absence of bacteria on the areas of theslide where no nanotubes were observed. There were only a few carbonnanotube nanostructured material observed at the periphery of the smear.The majority of the carbon nanotube nanostructured material had beenwashed from the slide when the excess violet stain was washed from theslide. Bacteria concentration was observed at boundaries of carbonnanotube nanostructured material (FIG. 3). The bacteria areas separateparticles as shown in violet.

Sample #4 also demonstrated presence of E. coli at boundaries of carbonnanotube nanostructured material but it appear in the image as blurspots (FIG. 4).

Atomic Force Microscopy Analysis

Atomic force microscopy (AFM) was made at Veeco Dimension 3100 ScanningProbe System in tapping mode.

Sample #2 demonstrated E. coli closely packed together (FIG. 5). Allcells had sharp boundaries. Note that the decrease in size and packingdensity of bacteria can be seen when comparing AFM image of sample #2before heat treatment (FIG. 5) and optical image of this sample afterheat treatment (FIG. 2).

Sample #3 shows some cells inside of carbon nanotube nanostructuredmaterial (FIG. 6). The presence at least one individual cell in uppermiddle part of the image is apparent. The boundary of the E. coli cellwall is diffused.

The disintegrating structure of the E. coli cell is also recognizable in3D image (FIG. 7). Also, we can see some diffused material within thecarbon nanotube nanostructured materials.

A larger surface area of sample #4 than is shown in FIG. 10 wasinvestigated and all of the E. coli cells are disintegrated beyond thepoint of recognition. However we can see the presence of diffused E.coli fragments within the carbon nanotube nanostructured material.

On ultrasonication in DI water of, E. coli and carbon nanotubenanostructured material, the two components agglomerateddue toelectrostatic and Van Der Waals forces. To the limit of detection, itwas observed that all bacteria in suspension were in contact with carbonnanotube nanostructured material, and adhered. There were no longer freeE. coli cells in Suspension #2.

The disintegration of the E. coli cells started immediately, or soonafter the cells come into intimate contact with the nanotubes. As aresult, the bacteria appeared to loose their sharp boundaries and theinternal contents of the bacteria appeared to spread out of the cell.The beginning of this process resulted after 3 hours of fixation (FIGS.6 and 8), and after 22 hours the spread went so far that it is difficultto recognize individual bacteria (FIG. 10).

Unless otherwise indicated, all numbers expressing quantities ofingredients, reaction conditions, and so forth used in the specificationand claims are to be understood as being modified in all instances bythe term “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention.

Other embodiments of the invention will be apparent to those skilled inthe art from consideration of the specification and practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with a true scope and spiritof the invention being indicated by the following claims.

1. A material for reducing contaminants in a fluid, said materialcomprising: carbon nanotubes, and a porous support medium for saidcarbon nanotubes, said porous support medium being permeable to the flowof said fluid, wherein a plurality of said carbon nanotubes comprise: alattice distortion, at least one functional group, and are fused orbonded to said porous support medium, to another carbon nanotube, or toa combination thereof.
 2. The material of claim 1, wherein said poroussupport medium comprises at least one component chosen from fibers,substrates, and particles.
 3. The material of claim 2, wherein saidfibers, substrates, and particles are chosen from ceramic and polymericmaterial.
 4. The material of claim 3, wherein said polymeric materialcomprises single or multi-component polymers, nylon, polyurethane,acrylic, methacrylic, polycarbonate, epoxy, silicone rubbers,polystyrene, polyethylene terephthalate, polybutylene terephthalate,poly-paraphylene terephtalamide, poly-(p-phenylene terephtalamide),polyester ester ketone, viton fluoroelastomer, poly-tetrafluoroethylene,polyvinylchloride, polyester, polypropylene, polychloroprene, acetates,and combinations thereof.
 5. The material of claim 4, wherein saidmulti-component polymers exhibit at least two different glass transitionor melting temperatures.
 6. The material of claim 3, wherein saidceramic material is chosen from at least one of the following: boroncarbide, boron nitride, boron oxide, boron phosphate, spinel, garnet,lanthanum fluoride, calcium fluoride, silicon carbide, carbon and itsallotropes, silicon oxide, glass, quartz, aluminum oxide, aluminumnitride, zirconium oxide, zirconium carbide, zirconium boride, zirconiumnitrite, hafnium boride, thorium oxide, yttrium oxide, magnesium oxide,phosphorus oxide, cordierite, mullite, silicon nitride, ferrite,sapphire, steatite, titanium carbide, titanium nitride, titanium boride,and combinations thereof.
 7. The material of claim 2, wherein saidparticles have a diameter up to 100 microns.
 8. The material of claim 1,wherein said carbon nanotubes are present in said material in an amountsufficient to reduce the concentration of contaminants in fluid thatcomes into contact with said material.
 9. The material of claim 1,wherein said carbon nanotubes are further doped or impregnated with anon-carbon nanotube material.
 10. The material of claim 1, wherein saidfunctional group comprises at least one organic functional group,inorganic functional group, or combinations thereof.
 11. The material ofclaim 10, wherein said functional group is attached to the surface ofsaid carbon nanotubes.
 12. The material of claim 11, wherein saidfunctional group is located on the ends of said carbon nanotubes and arepolymerized.
 13. The material of claim 10, wherein said at least oneorganic functional group comprises linear or branched, saturated orunsaturated groups.
 14. The material of claim 10, wherein said at leastone organic functional group comprises at least one chemical groupchosen from carboxyls, amines, polyamides, polyamphiphiles, diazoniumsalts, pyrenyls, silanes, and combinations thereof.
 15. The material ofclaim 10, wherein said at least one inorganic functional group comprisesat least one fluorine compound of boron, titanium, niobium, tungsten,and combination thereof.
 16. The material of claim 10, wherein said atleast one organic and inorganic functional groups comprise a halogenatom or halogenated compound.
 17. The material of claim 10, wherein saidcarbon nanotubes comprise a non-uniformity in composition and/or densityof functional groups across the surface of said carbon nanotubes and/oracross at least one dimension of said material.
 18. The material ofclaim 10, wherein said carbon nanotubes comprise a substantially uniformgradient of functional groups across the surface of said carbonnanotubes and/or across at least one dimension of said material.
 19. Thematerial of claim 1, wherein said carbon nanotubes have a scrolledtubular or non-tubular nano-structure of carbon rings.
 20. The materialof claim 19, wherein said carbon nanotubes having a scrolled tubular ornon-tubular nano-structure of carbon rings are single-walled,multi-walled, nanoscrolled or combinations thereof.
 21. The material ofclaim 19, wherein said carbon nanotubes having a scrolled tubular ornon-tubular nano-structure have a morphology chosen from nanohorns,cylindrical, nanospirals, dendrites, trees, spider nanotube structures,nanotube Y-junctions, and bamboo morphology.
 22. The material of claim1, wherein said fluid comprises at least one liquid or gas.
 23. Thematerial of claim 22, wherein said liquid comprises water.
 24. Thematerial of claim 22, wherein said of liquid is chosen from petroleumand its byproducts, biological fluids, foodstuffs, alcoholic beverages,and medicines.
 25. The material of claim 24, wherein said petroleum andits byproducts comprise aviation, automotive, marine, and locomotivefuels, rocket fuels, industrial and machine oils and lubricants, andheating oils and gases.
 26. The material of claim 24, wherein saidpetroleum and its by-products comprise aviation fuel and saidcontaminants comprise bacteria.
 27. The material of claim 24, whereinsaid biological fluids are derived from animals, humans, plants, orcomprise a growing broth used in the processing of a biotechnology orpharmaceutical product.
 28. The material of claim 24, wherein saidbiological fluids comprise blood, milk and components of both.
 29. Thematerial of claim 24, wherein said foodstuffs are chosen from animalby-products, fruit juice, natural syrups, and natural and synthetic oilsused in the cooking or food industry.
 30. The material of claim 24,wherein said animal by-products include milk and eggs.
 31. The materialof claim 24, wherein natural and synthetic oils used in the cooking orfood industry comprise olive oil, peanut oil, flower oils, and vegetableoils.
 32. The material of claim 24, wherein said alcoholic beveragescomprise beer, wine, or liquors.
 33. The material of claim 22, whereinsaid gas comprises the air.
 34. The material of claim 1, wherein saidcontaminants are chosen from at least one of the following: salts,metals, pathogens, microbiological organisms, DNA, RNA, natural organicmolecules, molds, fungi, and natural and synthetic toxins, endotoxins,proteins, and enzymes.
 35. The material of claim 34, wherein saidnatural and synthetic toxins comprise chemical and biological warfareagents.